Biogenic volatile organic compounds (BVOCs) in household cleaning products play key roles in indoor air quality (IAQ) because they are precursors for secondary pollutants formation. An accurate and rapid analytical technique for their measurement is of importance. This paper describes an optimization of a method for solid-phase microextraction (SPME) coupled with gas chromatography/mass spectrometry (GC-MS) for the determination of BVOCs. SPME fibers coated with Carboxen-PDMS are used to collect 12 individual BVOCs under standard conditions with a short exposure time of 5 min. Parameters influencing the extraction processes including sampling time, temperature and relative humidity are also investigated. All of the targeted BVOCs are shown to have limits of detection (LODs) in mixing ratios ranging from 0.31–0.50 ppbv, which are two magnitudes better than the LODs reported. The method precisions are between 1.1% and 6.7%. Comparison studies were carried out on a set of four floor cleaner extracts using the SPME method and traditional liquid injection method. Good agreement of the targeted BVOCs by the two methods was demonstrated. Our results indicated that SPME can serve as a simple and rapid sample collection approach to quantify BVOCs accurately and precisely in the indoor environment.